CN106977369A - It is a kind of to comprehensively utilize the device and method that electric energy combines methanol processed and ammonia - Google Patents
It is a kind of to comprehensively utilize the device and method that electric energy combines methanol processed and ammonia Download PDFInfo
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- CN106977369A CN106977369A CN201611160424.XA CN201611160424A CN106977369A CN 106977369 A CN106977369 A CN 106977369A CN 201611160424 A CN201611160424 A CN 201611160424A CN 106977369 A CN106977369 A CN 106977369A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/1512—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by reaction conditions
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/04—Preparation of ammonia by synthesis in the gas phase
- C01C1/0405—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst
- C01C1/0417—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst characterised by the synthesis reactor, e.g. arrangement of catalyst beds and heat exchangers in the reactor
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/1516—Multisteps
- C07C29/1518—Multisteps one step being the formation of initial mixture of carbon oxides and hydrogen for synthesis
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
Abstract
The device and method that electric energy combines methanol processed and ammonia is comprehensively utilized the invention discloses a kind of.Described device includes electricity generation system, water electrolysis hydrogen producing oxygen system, air-seperation system, system for methanol synthesis, ammonia synthesis system and oxygen storage tank, nitrogen storage tank, hydrogen-holder.The present invention is by electricity generation system, water electrolysis hydrogen producing oxygen system, air-seperation system, system for methanol synthesis, ammonia synthesis system and oxygen storage tank, nitrogen storage tank, the reasonable Arrangement of hydrogen-holder and comprehensive utilization, the problems such as abandoning wind, abandon light, abandon water of renewable energy power generation field can effectively be alleviated, the inexpensive large-scale comprehensive for realizing high safety, the on-site elimination of low cost and the energy of hydrogen is utilized, and specifies the low carbon development direction of coal chemical industry.Further, since present invention synthesis ammonia uses hydrogen in water electrolysis hydrogen producing oxygen, therefore, the dependence for producing hydrogen in traditional ammonia and methanol integrated production technique to coal gasification is broken away from, the ratio of ammonia alcohol can be adjusted flexibly, it is to avoid the dual waste of equipment and energy consumption.
Description
Technical field
The invention belongs to technical field of chemical engineering, and in particular to a kind of comprehensive utilization electric energy combines the dress of methanol processed and ammonia
Put and method.
Background technology
With pay attention to day by day the problems such as countries in the world are to energy security, ecological environment, climate change, accelerate development renewable
The energy has turned into international community and has promoted energy Transformation Development, the widespread consensus for tackling Global climate change and concerted activities.But,
Because there is the regenerative resources such as wind-powered electricity generation, photovoltaic the characteristics such as randomness, intermittence to have had a strong impact on the safe and stable operation of power network,
The problem of rationing the power supply that China's renewable energy power generation faces in recent years is on the rise, and future will realize the non-fossil energy of the year two thousand twenty 15%
Proportion target facing challenges are huge.National Energy Board's data display, 2015, China, which abandons wind rate, soared to 15%, Gansu Province
For 39%, light rate is abandoned close to three one-tenth in new peak in wound history, many provinces, and the small power station on the ground such as Yunnan abandons 500~60,000,000,000 kilowatts of electricity every year
When.While being to abandon wind, abandon light, abandon water etc. " three abandon persistent ailment " and be difficult to cure, the growth of another side fired power generating unit is but very fast
Suddenly.Further, since the problems such as regenerative resource such as wind-powered electricity generation, photovoltaic has randomness, intermittence, anti-peak regulation thus need thermoelectricity this
One stable power supply provides assistant service for it.Thermoelectricity participates in depth peak regulation then will burn 938.25 ten thousand tons of standard coals in 1 year more, no
Harm can be referred to as " abandoning coal ".With water power, wind-powered electricity generation, photovoltaic generation share increase, this " abandoning coal " can also increase, and this will enter
One step aggravates the discharge of greenhouse gases and taking place frequently for haze.
Although Large Copacity energy storage technology helps to solve the grid-connected problem of regenerative resource, it is ensured that electricity net safety stable is transported
OK, but existing energy-storage system is difficult to meet the need for new energy dissolves.And electricity turn gas technology then can will be comprising renewable
The higher hydrogen of purity is made by electrolysis water for the dump energy of the energy and traditional thermoelectricity or further methanation is input to naturally
It is transmitted, this novel energy-storing technology realizes transmission of the energy from power system to natural gas system, utilizes in feed channel
Extensive, the storage for a long time of existing natural gas real-time performance energy, strengthen power system and the coupling of natural gas system.
But hydrogen injection can cause tubing to natural gas line in terms of risk (hydrogen embrittlement and infiltration), therefore exist a definite limitation；And first
Alkanisation then has the problem of efficiency is relatively low.
Therefore, how to crack the contestation of benefits of traditional thermoelectricity and generation of electricity by new energy and thoroughly effect a radical cure " three abandon persistent ailment ",
The core bottleneck problem that electric Power Reform innovation and energy transition and upgrade must be broken through is pushed forward comprehensively as country.
On the other hand, the progress with social civilization and the prosperity of international economy, people are former to two big basic chemical industries
Material --- the demand of methanol and ammonia is growing, wherein 76,300,000 tons of methanol production capacity in 2015, synthesizes 83,000,000 tons of ammonia.So
And, the industrial production of methanol and ammonia belongs to coal base heavy chemical industry, is high pollution, high energy-consuming industry, there are a large amount of greenhouse gas
Body CO2、SO2, the PM2.5 such as nitrogen oxides discharge, be faced with the sternness from energy-saving and emission-reduction, ecological environment and water resources problems
Challenge, seriously threatens the health of the mankind.
In order to reduce toxic gas (CO, CO in syngas for synthetic ammonia2) concentration, reduce environmental pollution, 60 years 20th century
Synthesis ammonia " connection alcohol " technology is invented for the country, the nineties, synthesis ammonia " double first " technique skill was invented by rope company of Top of Denmark
Art, and applied to produce reality, there is energy-saving and environmental protection, consumption reduction, ammonia and methanol integrated production, on this basis domestic applications Shen
Please number 90105545.X, 93105920.8,94110903.8,96112370.2,02109000.9,200410014826.X,
200410094894.1 wait invention or utility model.These patented technologies lay particular emphasis on the purification function of syngas for synthetic ammonia, ammonia alcohol
The amplitude of accommodation of ratio is smaller.Patent No. ZL 200810018400.X " rich hydrocarbon industrial tail gas combined production of methanol, natural gas used for automobile
And the method for synthesis ammonia " effectively applied although making active principle and the energy obtain step, product proportion fixation can not be adjusted effectively
Section.A kind of publication number CN105296036 " synthesizing methanol, natural gas, the Poly-generation method of ammonia " and CN105209373 " coproduction
The method of ammonia, urea and methanol " then has equipment and technique not enough optimizes, replaceable selection is less and yield under abnormal conditions
The problems such as ratio is difficult to control.And publication number CN101429084 A " novel process for multistage synthesis of methanol with joint production of synthetic ammonia ",
CN105296036 A " a kind of synthesizing methanol, natural gas, the Poly-generation method of ammonia ", CN105753650 A " one kind synthesis ammonia, first
Alcohol co-production and device " uses water-gas for key component, exists that water resources consumption is excessive and CO2Greenhouse gases
The problem of utilization rate of excessive discharge and feed gas composition is relatively low.
The content of the invention
For deficiency of the prior art, it is an object of the invention to provide one kind comprehensive utilization electric energy combine methanol processed and
The device and method of ammonia.
To reach above-mentioned technical purpose, the present invention is achieved through the following technical solutions:
It is a kind of to comprehensively utilize the device that electric energy combines methanol processed and ammonia, wherein, including electricity generation system, water electrolysis hydrogen producing oxygen system
System, air-seperation system, system for methanol synthesis, ammonia synthesis system and oxygen storage tank, nitrogen storage tank, hydrogen-holder.
It is preferred that, the electricity generation system is renewable energy system or thermal power generation system；
The renewable energy system is wind generator system, solar power system, hydroelectric power system, nuclear energy
One kind or many in electricity generation system, biomass power generation system, system for geothermal production of electricity, tidal power generation system or sea wave power generation system
Kind；
The blower fan of the wind generator system is permanent magnet direct-drive Wind turbines, double-fed asynchronous Wind turbines or double-fed-straight drive
Mix Wind turbines；
The solar power system be mono-crystalline silicon solar electricity generation system, polycrystalline silicon solar power generation system, film too
One or more in positive energy electricity generation system or solar light-heat power-generation system.
It is preferred that, described water electrolysis hydrogen producing oxygen system is a water electrolysis hydrogen producing oxygen unit or multiple water electrolysis hydrogen producing oxygen
Unit；
Described water electrolysis hydrogen producing oxygen unit includes electrolytic cell assembly, gas-liquid separation device and hydrogen purification apparatus；
Described electrolytic cell assembly is alkaline water electrolytic cell, solid macromolecule electrolyte water electrolyser or high-temp solid oxidation
One or more in thing water electrolyser.
It is preferred that, the separation method of described air-seperation system is cryogenic air separation system, the separation of molecular sieve air
One or more in system or film space division air-seperation system.
It is preferred that, described cryogenic air separation system includes air compressor machine and condenser；
Described system for methanol synthesis includes coal gasifier, purifier, gas and adjusted than device, methyl alcohol synthetic reactor；
Described ammonia synthesis system includes gas and adjusted than device, ammonia convertor.
It is preferred that, the electric energy output end connection water electrolysis hydrogen producing oxygen system of the electricity generation system, air-seperation system, methanol
Synthesis system, ammonia synthesis system, for providing electric energy for each system；
The outlet of hydrogen purification apparatus in the water electrolysis hydrogen producing oxygen system is connected with hydrogen-holder entrance, the hydrogen
The outlet of storage tank adjusts the hydrogen inlet than device to connect with the gas in system for methanol synthesis all the way, another road and ammonia synthesis system
In gas adjust than device hydrogen inlet connect；
Oxygen outlet in the water electrolysis hydrogen producing oxygen system and the oxygen outlet in air-seperation system respectively with oxygen
Reservoir inlet is connected, the oxygen intake connection of the coal gasifier in the outlet and system for methanol synthesis of the oxygen storage tank；
Nitrogen outlet in the air-seperation system is connected with nitrogen storage tank entrance, the nitrogen storage tank outlet and ammino
The nitrogen inlet than device is adjusted to connect into the gas in system.
The method that electric energy combines methanol processed and ammonia is comprehensively utilized present invention also offers a kind of, following steps are specifically included：
(1) N that purity is higher than 99% is made by air-seperation system in air2It is higher than 99% O with purity2；
(2) H that purity is higher than 99.8% is made by water electrolysis hydrogen producing oxygen system in water2It is higher than 99.3% O with purity2, instead
The equation is answered to be：
(3) N made from step (1)2And a part of H made from part steps (2)2Adjusted by the gas in ammonia synthesis system
H-N ratio (H is obtained than device regulation2/N2) be 2.5~3.2 ammonia-synthesizing material gas, ammonia-synthesizing material gas is passed through ammonia synthesis system
In the ammonia convertor of system, ammonia is obtained by ammonia synthesis reaction, reaction equation is：
(4) by O made from step (1)2With O made from step (2)2Feeding methanol-fueled CLC system after being mixed in oxygen storage tank
The coal gasifier of system as coal gasification unstripped gas；
(5) unstripped gas of coal gasifier made from coal, water and step (4) is passed through into the coal gasifier in system for methanol synthesis
It is made and contains CO, CO2、H2Process gas；
(6) process gas made from step (5) is made after the purifier purification in system for methanol synthesis with step (2)
Another part H2Adjusted by the gas in system for methanol synthesis and be mixed to get hydrogen-carbon ratio than deviceFor 2.05~
2.2 methanol-fueled CLC unstripped gas, methanol-fueled CLC unstripped gas is passed through in methyl alcohol synthetic reactor and obtains methanol by methanol synthesis reaction,
Reaction equation is：
CO+2H2→CH3OH Δs H=-90.8kJ/mol
CO2+2H2→CH3OH+H2O Δs H=-49.5kJ/mol
It is preferred that, the reaction temperature of ammonia synthesis is 320~510 DEG C in step (3), and reaction pressure is 8.0~32MPa, is urged
Agent is iron-based, ferrous base or cobalt-base catalyst.
It is preferred that, the reaction temperature of methanol-fueled CLC is 200~300 DEG C in step (6), and reaction pressure is 3.0~16MPa,
Catalyst is copper-based catalysts.
It is preferred that, the purification technique in step (6) is cold process purification techniques or hot method purification techniques.
Relative to prior art, advantageous effects of the invention are：
(1) effectively abandoning wind, abandoning light, abandon water problems for renewable energy power generation field is alleviated：
From profound level, wind is abandoned, light is abandoned, abandons water problems and reflect the existing electric power development of China and operational mode increasingly
The present situation of the development of new energy is not suitable with, China's operation power mechanism, the deep-seated problems of power market are reflected.And from
Broadly, all " abandoning the energy " behaviors are all system problems, and coal industry is become with generation of electricity by new energy by competing with one another for
Depth cooperation, forms the road cracked that multipotency coupled system will be " three abandon " problem.Water electrolysis hydrogen producing oxygen device in the present invention
There is very strong adaptability to the unstability power output of wind-powered electricity generation, photovoltaic, the dump energy of regenerative resource is on the one hand logical
Cross water electrolysis hydrogen producing oxygen device change into can on a large scale, the hydrogen of long-time storage, be on the other hand the coal-based methanol of highly energy-consuming
Synthesis and ammonia synthesis provide the electric energy of low cost, realize the on-site elimination of regenerative resource, it is expected to effectively alleviate " three abandon " stupid
Disease.
(2) high safety of hydrogen, inexpensive on-site elimination are realized：
Hydrogen belongs to flammable explosive gas, with certain danger；It is high additionally, due to the big cost of light weight storage difficulty；And
High-pressure cylinder need to be injected it is fixed on long-tube trailer and realizes long-distance transportation, and transportation radius does not possess profit then more than 200km
Property, using scope by severely restricts.And the present invention need not be stored largely using hydrogen made from regenerative resource dump energy
Can large-scale low-cost supply coal chemical industry nearby and dissolve, overcome hydrogen high-risk in traditional hydrogen energy-storage system, low cost, big rule
Mould is stored and the difficult limitation of long-distance sand transport, has expanded the approach and scale of renewable energy utilization.
(3) the inexpensive large-scale comprehensive for realizing energy is utilized：
Not only wind-resources and solar energy resources are abundant for three northern areas of China, are also main coal district.The present invention is by wind energy, the sun
Can equal energy source change into Hydrogen Energy, and it is former to convert coal into via coal chemical industry the derived energy chemical on the basis such as methanol and ammonia nearby
Material, realizes the extensive on-site elimination of low cost and the comprehensive utilization of the various energy.
(4) the cleaning conversion of coal is realized, the direction of coal chemical industry low carbon development is specified：
Traditional coal radical synthesizing methanol and ammonia are needed using water-gas as raw material, in the case of no external hydrogen source
Pass through the hydrogen-carbon ratio of process gas made from coal baseTherefore need to remove unnecessary CO2, and pass through water electrolysis system
The obtained hydrogen of hydrogen-oxygen device conversion is mixed with process gas can improve hydrogen-carbon ratio, thus improve the utilization rate of process gas component,
CO conversion has been broken away from again and has adjusted hydrogen process, makes CO2Greenhouse gases are from source emission reduction.
On the other hand, coal radical synthesizing methanol and ammonia are the industries that high pollution and highly energy-consuming are laid equal stress on, what traditional handicraft was used
Electric energy is the electricity of the bulk power grid based on serious pollution thermal power generation, thus in terms of whole big system perspective is that coal industry is high
The secondary superposition of pollution, this means that the bigger pollution of production capacity is more serious.And the present invention can use renewable energy power generation for
It is main, electric scheme is adopted supplemented by thermoelectricity power network, the inexpensive high definition clean conversion of coal is truly realized.Thus the present invention is coalification
The low-carbon of work opened one efficiently, the integrated developing direction in cleaning, high added value, base.
(5) ammonia alcohol product proportion is flexibly adjustable：
Hydrogen in water electrolysis hydrogen producing oxygen is used during present invention synthesis ammonia, has thoroughly been broken away from traditional ammonia and methanol integrated production technique
The dependence of hydrogen is produced to coal gasification, so that ammonia-alcohol ratio example can be adjusted flexibly according to the actual requirements, it is to avoid equipment and
The dual waste of energy consumption.
Brief description of the drawings
Fig. 1 is the process chart for the method that electric energy of the present invention comprehensively utilizes joint methanol processed and ammonia.
Fig. 2 is the process chart for the method that wind-powered electricity generation of the present invention comprehensively utilizes joint methanol processed and ammonia.
Fig. 3 is process chart of the solar energy composite of the present invention using the method for combining methanol processed and ammonia.
Fig. 4 be wind-powered electricity generation of the present invention (straight drive blower) and solar energy (polysilicon photovoltaic array) comprehensively utilize combine methanol processed and
The process chart of the method for ammonia.
Fig. 5 is wind-powered electricity generation of the present invention (double-fed blower fan) and solar energy (film photovoltaic array) comprehensive utilization joint methanol processed and ammonia
Method process chart.
Fig. 6 is the process chart for the method that water power of the present invention comprehensively utilizes joint methanol processed and ammonia.
Embodiment
The invention will now be further described with reference to specific embodiments, advantages of the present invention and feature will be with description and
It is apparent.But embodiment is only exemplary, does not constitute any limitation to the scope of the present invention.Those skilled in the art should
It should be appreciated that, the details and form of technical solution of the present invention can be repaiied without departing from the spirit and scope of the invention
Change or replace, but these modifications and replacement are each fallen within protection scope of the present invention.
Ammonia-synthesizing material gas and methanol-fueled CLC new raw material gas meet following condition in each embodiment：Hydrogen in ammonia-synthesizing material gas
Nitrogen ratio (H2/N2) it is 2.5~3.2, methanol-fueled CLC unstripped gas hydrogen-carbon ratioFor 2.05~2.2.
The electric energy of embodiment 1 comprehensive utilization joint methanol processed and ammonia
It is the electricity using the one or more kinds of forms for including renewable energy power generation and traditional thermal power generation as shown in Figure 1
Water electrolysis into hydrogen and oxygen and by air can be separated into nitrogen and oxygen by air-seperation system；Three kinds of gas difference
Press-in gas reservoir enters row buffering and standby；The oxygen of oxygen storage tank be all passed through the coal gasifier of system for methanol synthesis and coal,
Form methanol technics gas after water reaction purification and adjusted subsequently into the gas of system for methanol synthesis and compare device；A part for hydrogen-holder
Hydrogen be passed through the gas of system for methanol synthesis adjust than in device with methanol technics controlled atmosphere into the suitable methanol-fueled CLC raw material of hydrogen-carbon ratio
Gas, afterwards methanol-fueled CLC unstripped gas enter methyl alcohol synthetic reactor carry out methanol synthesis reaction, obtain methanol finally by rectifying；Hydrogen
The gas tune that another part hydrogen of storage tank and all nitrogen of nitrogen storage tank each lead into ammonia synthesis system is mixed into than device
The suitable ammonia-synthesizing material gas of H-N ratio, then ammonia-synthesizing material gas obtain ammonia into ammonia convertor.
The wind-powered electricity generation of embodiment 2 comprehensive utilization joint methanol processed and ammonia
As shown in Fig. 2 being used as electricity by the use of the local wind-powered electricity generation produced equipped with double-fed asynchronous Wind turbines wind field in northeast somewhere
Power is supplied, and the mass concentration prepared by deionized water is passed through in alkaline water electrolytic cell for the 30wt% KOH aqueous solution and carries out electricity
Xie Shui, the air-water mixture come out from electrolytic cell enters purity of the gas-liquid separation device produced by after gas-liquid separation and is
99.3% oxygen is directly entered oxygen storage tank, and the hydrogen produced by after gas-liquid separation enters purification devices by after purification
(purity reaches 99.8%) enters hydrogen-holder；Air is pressed into what air-seperation system was produced after the separation of cryogenic refrigeration method
Purity enters oxygen storage tank for 99.5% oxygen, and the purity of generation enters nitrogen storage tank for 99.5% nitrogen.
Oxygen in water-coal-slurry and oxygen storage tank is each led into progress gasification reaction in coal gasifier to obtain containing CO, CO2、
H2Process gas (CO：40~50%, H2：35~40%, CO2：5~10%, N2+CH4＜ 0.5%), process gas enters purification and filled
Put and purified, the hydrogen partial in the process gas and hydrogen-holder after purification is each led into gas tune is deployed into first than device
Alcohol synthetic raw gas (CO：25~28%, H2：69~70%, CO2：3~5%, N2+CH4＜ 0.5%), by methanol-fueled CLC raw material
Gas, which is passed through in methyl alcohol synthetic reactor, carries out methanol synthesis reaction, and refined methanol product is obtained finally by rectifying, and refined methanol is made and meets
National standard GB338 requirement.The condition of methanol synthesis reaction is this area normal condition：Reaction temperature is 200~300 DEG C, reaction
Pressure is 3.0~16.0MPa, and catalyst is copper-based catalysts.
The gas that hydrogen partial in nitrogen and hydrogen-holder in nitrogen storage tank is each led into ammonia synthesis system is adjusted
H-N ratio (H is deployed into than device2/N2) be 2.5~3.2 ammonia-synthesizing material gas, ammonia-synthesizing material gas is passed through ammonia synthesis system
Ammonia convertor in carry out ammonia synthesis reaction finally obtain ammonolysis product.The condition of ammonia synthesis reaction is this area normal condition：Instead
It is 320~510 DEG C to answer temperature, and reaction pressure is 8~32MPa, and catalyst is iron-based, ferrous base or cobalt-base catalyst.
The solar energy composite of embodiment 3 utilizes joint methanol processed and ammonia
As shown in figure 3, being sent in In A Certain Place of Xinjiang using the local photovoltaic DC field equipped with polysilicon solar cell plate array
Electric energy as supply of electric power, the mass concentration prepared by deionized water is passed through alkaline water power for the 30wt% KOH aqueous solution
Electrolysis water is carried out in solution groove, the air-water mixture come out from electrolytic cell enters gas-liquid separation device produced by after gas-liquid separation
Purity be directly entered oxygen storage tank for 99.3% oxygen, the hydrogen produced by after gas-liquid separation enters purification devices warp
Cross (purity reaches 99.8%) after purification and enter hydrogen-holder；Air is pressed into air-seperation system to separate by cryogenic refrigeration method
The purity produced afterwards enters oxygen storage tank for 99.5% oxygen, and the purity of generation enters nitrogen storage tank for 99.5% nitrogen.
Oxygen in water-coal-slurry and oxygen storage tank is each led into progress gasification reaction in coal gasifier to obtain containing CO, CO2、
H2Etc. the process gas (CO of main component：40~50%, H2：35~40%, CO2：5~10%, N2+CH4＜ 0.5%), process gas
Purified into purifier, the hydrogen partial in the process gas and hydrogen-holder after purification is each led into gas adjusts than dress
Put and be deployed into methanol-fueled CLC unstripped gas (CO：25~28%, H2：69~70%, CO2：3~5%, N2+CH4＜ 0.5%), by first
Alcohol synthetic raw gas, which is passed through in methyl alcohol synthetic reactor, carries out methanol synthesis reaction, obtains refined methanol product finally by rectifying, is made
Refined methanol meets national standard GB338 requirement.The condition of methanol synthesis reaction is this area normal condition：Reaction temperature be 200~
300 DEG C, reaction pressure is 3.0~16.0MPa, and catalyst is copper-based catalysts.
The gas that hydrogen partial in nitrogen and hydrogen-holder in nitrogen storage tank is each led into ammonia synthesis system is adjusted
H-N ratio (H is deployed into than device2/N2) be 2.5~3.2 ammonia-synthesizing material gas, ammonia-synthesizing material gas is passed through ammonia synthesis system
Ammonia convertor in carry out ammonia synthesis reaction finally obtain ammonolysis product.The condition of ammonia synthesis reaction is this area normal condition：Instead
It is 320~510 DEG C to answer temperature, and reaction pressure is 8~32MPa, and catalyst is iron-based, ferrous base or cobalt-base catalyst.
The wind-powered electricity generation of embodiment 4 (straight drive blower) and solar energy (polysilicon photovoltaic array) comprehensive utilization joint methanol processed and ammonia
As shown in figure 4, being equipped with the wind-powered electricity generation of permanent magnet direct-drive Wind turbines wind field generation using locality in Inner Mongol somewhere and being equipped with
The electric energy that polysilicon solar cell plate array is produced is supplied as combined power, is by the mass concentration prepared by deionized water
The 30wt% KOH aqueous solution, which is passed through in alkaline water electrolytic cell, carries out electrolysis water, and the air-water mixture come out from electrolytic cell enters gas
Purity of the liquid separating apparatus produced by after gas-liquid separation is directly entered oxygen storage tank for 99.3% oxygen, by gas-liquid point
Enter hydrogen-holder by (purity reaches 99.8%) after purification into purification devices from rear produced hydrogen；Air is pressed into
Air-seperation system purity for producing after the separation of cryogenic refrigeration method enters oxygen storage tank for 99.5% oxygen, generation it is pure
Spend and enter nitrogen storage tank for 99.5% nitrogen.
Oxygen in water-coal-slurry and oxygen storage tank is each led into progress gasification reaction in coal gasifier to obtain containing CO, CO2、
H2Etc. the process gas (CO of main component：40~50%, H2：35~40%, CO2：5~10%, N2+CH4＜ 0.5%), process gas
Purified into purifier, the hydrogen partial in the process gas and hydrogen-holder after purification is each led into gas adjusts than dress
Put and be deployed into methanol-fueled CLC unstripped gas (CO：25~28%, H2：69~70%, CO2：3~5%, N2+CH4＜ 0.5%), by first
Alcohol synthetic raw gas, which is passed through in methyl alcohol synthetic reactor, carries out methanol synthesis reaction, obtains refined methanol product finally by rectifying, is made
Refined methanol meets national standard GB338 requirement.The condition of methanol synthesis reaction is this area normal condition：Reaction temperature be 200~
300 DEG C, reaction pressure is 3.0~16.0MPa, and catalyst is copper-based catalysts.
The gas that hydrogen partial in nitrogen and hydrogen-holder in nitrogen storage tank is each led into ammonia synthesis system is adjusted
H-N ratio (H is deployed into than device2/N2) be 2.5~3.2 ammonia-synthesizing material gas, ammonia-synthesizing material gas is passed through ammonia synthesis system
Ammonia convertor in carry out ammonia synthesis reaction finally obtain ammonolysis product.The condition of ammonia synthesis reaction is this area normal condition：Instead
It is 320~510 DEG C to answer temperature, and reaction pressure is 8~32MPa, and catalyst is iron-based, ferrous base or cobalt-base catalyst.
The wind-powered electricity generation of embodiment 5 (double-fed blower fan) and solar energy (film photovoltaic array) comprehensive utilization joint methanol processed and ammonia
As shown in figure 5, being equipped with the wind-powered electricity generation of double-fed asynchronous Wind turbines wind field generation using locality in Gansu somewhere and being equipped with
The electric energy that thin-film solar panel array is produced is supplied as combined power, is by the mass concentration ratio prepared by deionized water
The 30wt.% KOH aqueous solution, which is passed through in alkaline water electrolytic cell, carries out electrolysis water, and the air-water mixture come out from electrolytic cell enters gas
Purity of the liquid separating apparatus produced by after gas-liquid separation is directly entered oxygen storage tank for 99.3% oxygen, by gas-liquid point
Enter hydrogen-holder by (purity reaches 99.8%) after purification into purification devices from rear produced hydrogen；Air is pressed into
Air-seperation system purity for producing after the separation of cryogenic refrigeration method enters oxygen storage tank for 99.5% oxygen, generation it is pure
Spend and enter nitrogen storage tank for 99.5% nitrogen.
Oxygen in water-coal-slurry and oxygen storage tank is each led into progress gasification reaction in coal gasifier to obtain containing CO, CO2、
H2Etc. the process gas (CO of main component：40~50%, H2：35~40%, CO2：5~10%, N2+CH4＜ 0.5%), process gas
Purified into purifier, the hydrogen partial in the process gas and hydrogen-holder after purification is each led into gas adjusts than dress
Put and be deployed into methanol-fueled CLC unstripped gas (CO：25~28%, H2：69~70%, CO2：3~5%, N2+CH4＜ 0.5%), by first
Alcohol synthetic raw gas, which is passed through in methyl alcohol synthetic reactor, carries out methanol synthesis reaction, obtains refined methanol product finally by rectifying, is made
Refined methanol meets national standard GB338 requirement.The condition of methanol synthesis reaction is this area normal condition：Reaction temperature be 200~
300 DEG C, reaction pressure is 3.0~16.0MPa, and catalyst is copper-based catalysts.
The gas that hydrogen partial in nitrogen and hydrogen-holder in nitrogen storage tank is each led into ammonia synthesis system is adjusted
H-N ratio (H is deployed into than device2/N2) be 2.5~3.2 ammonia-synthesizing material gas, ammonia-synthesizing material gas is passed through ammonia synthesis system
Ammonia convertor in carry out ammonia synthesis reaction finally obtain ammonolysis product.The condition of ammonia synthesis reaction is this area normal condition：Instead
It is 320~510 DEG C to answer temperature, and reaction pressure is 8~32MPa, and catalyst is iron-based, ferrous base or cobalt-base catalyst.
The water power of embodiment 6 comprehensive utilization joint methanol processed and ammonia
As shown in fig. 6, the electric energy produced in Yunnan somewhere by the use of local small power station is supplied as combined power, by electrical conductivity
It is passed through in solid macromolecule electrolyte water electrolyser for 1M Ω deionized water and carries out electrolysis water, the air water come out from electrolytic cell is mixed
Compound enters purity of the gas-liquid separation device produced by after gas-liquid separation and enters oxygen storage tank for 99.7% oxygen, passes through
Purity produced by after gas-liquid separation enters hydrogen-holder for 99.9% hydrogen；Air is pressed into air-seperation system through too deep
The purity produced after degree freezing separation enters oxygen storage tank for 99.5% oxygen, and the purity of generation is entered for 99.5% nitrogen
Enter nitrogen storage tank.
Oxygen in fine coal, water vapour and oxygen storage tank is each led into progress gasification reaction in powder coal gasification furnace to be contained
CO、CO2、H2Etc. the process gas (CO of main component：40~50%, H2：35~40%, CO2：5~10%, N2+CH4＜ 0.5%),
Process gas is purified into purifier, and the hydrogen partial in the process gas and hydrogen-holder after purification is each led into gas
Tune is deployed into methanol-fueled CLC unstripped gas (CO than device：25~28%, H2：69~70%, CO2：3~5%, N2+CH4＜
0.5%), methanol-fueled CLC unstripped gas is passed through in methyl alcohol synthetic reactor and carries out methanol synthesis reaction, smart first is obtained finally by rectifying
Alcohol product, obtained refined methanol meets national standard GB338 requirement.The condition of methanol synthesis reaction is this area normal condition：Reaction
Temperature is 200~300 DEG C, and reaction pressure is 3.0~16.0MPa, and catalyst is copper-based catalysts.
The gas that hydrogen partial in nitrogen and hydrogen-holder in nitrogen storage tank is each led into ammonia synthesis system is adjusted
H-N ratio (H is deployed into than device2/N2) be 2.5~3.2 ammonia-synthesizing material gas, ammonia-synthesizing material gas is passed through ammonia synthesis system
Ammonia convertor in carry out ammonia synthesis reaction finally obtain ammonolysis product.The condition of ammonia synthesis reaction is this area normal condition：Instead
It is 320~510 DEG C to answer temperature, and reaction pressure is 8~32MPa, and catalyst is iron-based, ferrous base or cobalt-base catalyst.
Embodiments of the invention content is disclosed above, but the present embodiment is not limited to the scope that the present invention is implemented,
The simple equivalent changes and modifications made according to claims of the present invention and description, still falls within the technology of the present invention side
In the range of case.
Claims (10)
1. a kind of comprehensively utilize the device that electric energy combines methanol processed and ammonia, it is characterised in that including electricity generation system, water electrolysis hydrogen producing
Oxygen system, air-seperation system, system for methanol synthesis, ammonia synthesis system and oxygen storage tank, nitrogen storage tank, hydrogen-holder.
2. comprehensive utilization electric energy combines the device of methanol processed and ammonia as claimed in claim 1, it is characterised in that：
The electricity generation system is renewable energy system or thermal power generation system；
The renewable energy system is wind generator system, solar power system, hydroelectric power system, nuclear energy power generation
One or more in system, biomass power generation system, system for geothermal production of electricity, tidal power generation system or sea wave power generation system；
The blower fan of the wind generator system is that permanent magnet direct-drive Wind turbines, double-fed asynchronous Wind turbines or double-fed-straight drive mix
Wind turbines；
The solar power system is mono-crystalline silicon solar electricity generation system, polycrystalline silicon solar power generation system, thin film solar
One or more in electricity generation system or solar light-heat power-generation system.
3. comprehensive utilization electric energy combines the device of methanol processed and ammonia as claimed in claim 1, it is characterised in that：
Described water electrolysis hydrogen producing oxygen system is a water electrolysis hydrogen producing oxygen unit or multiple water electrolysis hydrogen producing oxygen units；
Described water electrolysis hydrogen producing oxygen unit includes electrolytic cell assembly, gas-liquid separation device and hydrogen purification apparatus；
Described electrolytic cell assembly is alkaline water electrolytic cell, solid macromolecule electrolyte water electrolyser or high-temperature solid oxide water
One or more in electrolytic cell.
4. comprehensive utilization electric energy combines the device of methanol processed and ammonia as claimed in claim 1, it is characterised in that described air
Piece-rate system is one kind or many in cryogenic air separation system, molecular sieve air-seperation system or film space division air-seperation system
Kind.
5. comprehensive utilization electric energy combines the device of methanol processed and ammonia as claimed in claim 1, it is characterised in that：
Described cryogenic air separation system includes air compressor machine and condenser；
Described system for methanol synthesis includes coal gasifier, purifier, gas and adjusted than device, methyl alcohol synthetic reactor；
Described ammonia synthesis system includes gas and adjusted than device, ammonia convertor.
6. the comprehensive utilization electric energy as described in claim any one of 1-5 combines the device of methanol processed and ammonia, it is characterised in that：
The electric energy output end connection water electrolysis hydrogen producing oxygen system of the electricity generation system, air-seperation system, system for methanol synthesis, ammonia
Synthesis system, for providing electric energy for each system；
The outlet of hydrogen purification apparatus in the water electrolysis hydrogen producing oxygen system is connected with hydrogen-holder entrance, the hydrogen-holder
Outlet adjust connect than the hydrogen inlet of device with the gas in system for methanol synthesis all the way, in another road and ammonia synthesis system
Gas adjusts the hydrogen inlet than device to connect；
Oxygen outlet in the water electrolysis hydrogen producing oxygen system and the oxygen outlet in air-seperation system respectively with oxygen storage tank
Entrance is connected, the oxygen intake connection of the coal gasifier in the outlet and system for methanol synthesis of the oxygen storage tank；
Nitrogen outlet in the air-seperation system is connected with nitrogen storage tank entrance, the nitrogen storage tank outlet and ammonia synthesis system
Gas in system adjusts the nitrogen inlet than device to connect.
7. a kind of comprehensively utilize the method that electric energy combines methanol processed and ammonia, it is characterised in that comprises the following steps：
(1) N that purity is higher than 99% is made by air-seperation system in air2It is higher than 99% O with purity2；
(2) H that purity is higher than 99.8% is made by water electrolysis hydrogen producing oxygen system in water2It is higher than 99.3% O with purity2, reaction side
Formula is：
(3) N made from step (1)2And a part of H made from part steps (2)2Adjusted by the gas in ammonia synthesis system than dress
Put regulation and obtain H-N ratio (H2/N2) be 2.5~3.2 ammonia-synthesizing material gas, ammonia-synthesizing material gas is passed through ammonia synthesis system
In ammonia convertor, ammonia is obtained by ammonia synthesis reaction, reaction equation is：
(4) by O made from step (1)2With O made from step (2)2Feeding system for methanol synthesis after being mixed in oxygen storage tank
Coal gasifier as coal gasification unstripped gas；
(5) unstripped gas of coal gasification made from coal, water and step (4) is made by the coal gasifier in system for methanol synthesis and contained
CO、CO2、H2Process gas；
(6) by process gas made from step (5) after the purifier purification in system for methanol synthesis with it is another made from step (2)
A part of H2Adjusted by the gas in system for methanol synthesis and be mixed to get hydrogen-carbon ratio than deviceFor 2.05~2.2
Methanol-fueled CLC unstripped gas, methanol-fueled CLC unstripped gas is passed through in methyl alcohol synthetic reactor and obtains methanol by methanol synthesis reaction, reaction
Equation is：
CO+2H2→CH3OH Δs H=-90.8kJ/mol
CO2+2H2→CH3OH+H2O Δs H=-49.5kJ/mol.
8. comprehensive utilization electric energy combines the method for methanol processed and ammonia as claimed in claim 7, it is characterised in that in step (3)
The reaction temperature of ammonia synthesis is 320~510 DEG C, and reaction pressure is 8.0~32MPa, and catalyst is that iron-based, ferrous base or cobalt-based are urged
Agent.
9. comprehensive utilization electric energy combines the method for methanol processed and ammonia as claimed in claim 7, it is characterised in that in step (6)
The reaction temperature of methanol-fueled CLC is 200~300 DEG C, and reaction pressure is 3.0~16MPa, and catalyst is copper-based catalysts.
10. comprehensive utilization electric energy combines the method for methanol processed and ammonia as claimed in claim 7, it is characterised in that in step (6)
Purification technique be cold process purification techniques or hot method purification techniques.
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